CN103848738B - Polymerizable compound and purposes in a liquid crystal display thereof - Google Patents

Abstract

The present invention relates to polymerizable compound, its preparation method and intermediate thereof, with it for optics, electrooptics and the purposes of electronics purpose, particularly in liquid crystal (FK) medium and liquid crystal display, the especially purposes in the liquid crystal display of PS or PSA (" polymer stabilizing " or " polymer-stabilized alignment ") type.

Description

Polymerizable compound and purposes in a liquid crystal display thereof

The application is the divisional application of the Chinese patent application of Application No. 201080048338.4.

Invention field

The present invention relates to polymerizable compound, its preparation method and intermediate thereof, and it is for optics, electrooptics or electronics The purposes of purpose, particularly in liquid crystal (FK) medium and liquid crystal display, especially PS or PSA (" polymer stabilizing " or " polymer-stabilized alignment ") type liquid crystal display in purposes.

Background technology

Currently used liquid crystal display (FK-display) is mainly those of TN (twisted-nematic) type.But, they tools There is the defect of striking contrast degree view angle dependency.Additionally, it is known that the so-called VA (vertical orientation) with broader visual angle shows Show device.The liquid crystal cell of VA display contains the layer of liquid crystal media between two transparency electrodes, and wherein this liquid crystal media generally has There is negative dielectric (DK-) anisotropy value.In the power-off state, the molecule of liquid crystal layer with being perpendicular to electrode surface (vertical plane ground) or Tilt vertical plane ground (English " tilted ") orientation.When applying a voltage on two electrodes, occur liquid crystal molecules parallel in electricity The reorientation of pole-face.

Additionally, it is known that OCB (optical compensation curved) display, it has so-called " curved based on birefringence effect and having Bent " it is orientated and the most positive (DK-) anisotropic liquid crystal layer.When applying voltage, liquid crystal molecule is occurred to be perpendicular to electrode surface Reorientation.It addition, OCB display usually contains one or more Birefringent optical phase shift films, " curved in the dark state to prevent Bent " the less desirable photopermeability of box.OCB display has broader visual angle and shorter response time relative to TN display (Schaltzeiten).

It is also known that have so-called IPS (in-plane switching) display, it contains the liquid crystal layer between two substrates, its In two electrodes be solely positioned on in two substrates, and preferably there is pectinate texture interlaced with each other.Thus executing Power up when being pressed onto electrode, produce the electric field with the significant component being parallel to liquid crystal layer between which.Liquid crystal is so caused to divide Son reorientation in aspect.

It addition, propose so-called FFS (fringing field switching) display (referring particularly to S.H.Jung etc., Jpn.J.Appl.Phys., volume 43, No.3,2004,1028), its equally in same substrate containing two electrodes, but not Being same as IPS display, only one of which is configured to the electrode form of pectinate texture, and another electrode is non-structured.By This produces strong so-called " fringing field ", the highfield at the most adjacent electrode edge, and produces electric field, this electricity in whole box Field has strong vertical component and strong horizontal component simultaneously.Both IPS display and FFS display have the least contrast Degree view angle dependency.

In the VA display of newer type, it is multiple less that the homogeneous orientation of liquid crystal molecule is limited within liquid crystal cell FarmlandOn.Can exist to mistake between these farmlands (also referred to as tilt domain (English " tilt domains ")) (Disklinationen).There is the VA display of tilt domain, relative to tradition VA display, there is bigger contrast and ash The visual angle of degree is not dependent.It addition, this display is easier to preparation, because being no longer needed for making in an on state molecule The extra treatment of electrode surfaces (such as by friction) of homogeneous orientation.Replace this place, controlled by the particular configuration of electrode Inclination angle or the preferential sensing of inclination angle (English " (pretilt) of pre-tilt ").

In so-called MVA (multi-zone vertical alignment nematic) display, this point generally causes local pre-dumping by making electrode have Oblique projection or projection (English " protrusions ") realize.Thus, when applying voltage in different, specific box district Liquid crystal molecules parallel is made to be orientated in electrode surface in territory in different directions.It is achieved in " controlled " switching, and prevents interference The formation to wrong line.Although this arrangement improves the visual angle of display, but cause the reduction of its light transmission.

MVA improves the projection only employed on an electrode side further, and opposed electrode has otch (English " slits "), which improve light transmission.The electrode of this otch produces uneven electric field when applying voltage in liquid crystal cell, makes Controlled switching must be furthermore achieved that.For improving light transmission further, the spacing between otch and projection can be expanded, but this Cause again the prolongation of response time.In so-called PVA (patterning VA), need not projection the most feasible, its mode is to pass through Two electrodes carry out structuring by otch on opposite side, and this causes the light transmission of contrast and the improvement increased, but this Be technically difficulty and make display more sensitive to mechanical influence (pat, English " tapping " etc.).But for many Application, such as monitor and especially TV-screen, it is desirable to shorten response time and improve contrast and the brightness of display (absorbance).

Another kind of development is so-called PS or PSA (" polymer stabilizing " or " polymer-stabilized alignment ") display, to it Term " polymer " is used to stablize (polymer stabilized) the most once in a while ".In these display, by a small amount of (such as 0.3 Weight %, typically < 1 weight %) one or more polymerizable compounds be added in liquid crystal media, and after being filled with liquid crystal cell It is between electrode to apply or do not apply under voltage condition, to make its in-situ polymerization or crosslinking (generally by UV photopolymerization).Can gather The mesomorphic or the liquid-crystal compounds (also referred to as reactive mesogen or " RM ") that close are added in liquid crystal compound have proven to be particularly suitable 's.

Unless otherwise directed, below term " PSA " is used for apparently PS display and PSA display.

Meanwhile, PS (A) principle is used for various traditional liquid crystal display.It is thus possible, for instance known PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS and PSA-TN display.In the case of PSA-VA and PSA-OCB display, polymerizable compound Polymerization preferably apply voltage under carry out, for during PSA-IPS display with and without executing alive situation Under carry out.As can verify in testing cassete, PS (A) method causes the pre-tilt in box.Such as, with regard to PSA-OCB The situation of display, it is possible to achieve warp architecture is subject to stable, thus not having bias voltage is also enough or can be by It reduces.With regard to the situation of PSA-VA display, this pre-tilt has positive effect to response time.For PSA-VA display, MVA or PVA pixel and the electrode lay-out of standard can be used.But, it addition, such as do not have only with a structurized electrode side It can also be enough for having projection, which considerably simplifies production and creates fabulous contrast simultaneously, having fabulous simultaneously Light transmission.

Also, it has proven that so-called positivity-VA display (" Positiv-VA ") is specially suitable embodiment.Just As the situation at traditional VA display, in positivity-VA display, the initial orientation of liquid crystal is at stressless initial shape It is vertical plane under state, is i.e. substantially perpendicular to substrate.But, contrary with traditional VA display, positivity-VA display uses There is the liquid crystal media of positive dielectric anisotropy.Such as the situation at normally used IPS display, show at positivity-VA Two electrodes in device are positioned only in one of them of two substrates, and it is (interdigital preferably to have comb shape interlaced with each other Type) structure.By applying voltage (it produces and is arranged essentially parallel to the field of liquid crystal media layer) on interdigitated electrodes, by liquid crystal Molecular conversion is the orientation being arranged essentially parallel to substrate.Even if having proven to polymer stabilising (PSA) in positivity VA display Being also advantageous, i.e. add RM in liquid crystal media, they are polymerized in box, thus can realize the notable fall of response time Low.

PSA-VA display is described in such as JP10-036847A, EP1170626A2, US6,861,107, US7,169, 449, in US2004/0191428A1, US2006/0066793A1 and US2006/0103804A1.PSA-OCB display is such as retouched State at T.-J-Chen etc., Jpn.J.Appl.Phys.45,2006,2702-2704 and S.H.Kim, L.-C-Chien, In Jpn.J.Appl.Phys.43,2004,7643-7647.PSA-IPS display be described in such as US6,177,972 and Appl.Phys.Lett.1999,75 (21), in 3264.PSA-TN display is described in such as Optics Express2004,12 (7), in 1221.

Such as above-mentioned conventional LCD device, PSA display can also serve as active matrix or passive matrix display comes Operation.For the situation of Active Matrix Display, single pixel is generally by integrated non-linear active element such as transistor (such as thin film transistor (TFT), English " thin film transistor " or " TFT ") is addressed, and shows with regard to passive matrix For the situation of device, carrying out generally according to multiple transmission method, two of which method is all well known in the prior art.

Apply especially for monitor and particularly TV, require response time and liquid crystal display as beforely Contrast and the optimization of brightness (that is being also transmittance).PSA method can be in the benefit of key provided herein.Especially for For PSA-VA, PSA-IPS, PSA-FFS and PSA-positivity-VA display, pre-tilt measurable in testing cassete is relevant The shortening of response time can realize in the case of other parameter is not had obvious damage.

In the prior art, for example with the polymerizable compound of following formula

Wherein P represents polymerisable group, it is common that acrylate or methacrylic acid ester group, such as US7,169, Described in 449.

But create problem, not every by liquid crystal compound (being also hereinafter referred to as " liquid crystal host mixture ")+ The combination that polymerizable components (usually RM) forms is suitable for PSA display, because such as can not regulating acquisition and tilting or abundant Inclination, or " voltage keep than " (VHR or HR) is not enough to apply for TFT display because the most so-called.Additionally, It is found that in PSA display time, known liquid crystal compound and RM still have some defects from the prior art.Cause This, be not that the RM dissolving in liquid crystal compound known to each is suitable for PSA display.Additionally, except directly measuring Outside pre-tilt in PSA display, it is often difficult to find the suitable selection standard for RM.If it is desire to by means of UV light Being added without (some application is probably favourable by this) when light trigger is polymerized, the selection of suitable RM becomes the least.

It addition, the combination of selected liquid crystal host mixture/RM should have alap rotary viscosity and as far as possible Good electrical property, particularly, it should have the highest VHR.In PSA display, it is especially desirable to using UV photoirradiation High VHR afterwards, because UV exposure is requisite part in display production process, but also in the display fortune made Occur as normal load (Belastung) between the departure date.

Particularly, the available new material with the PSA display for producing the least pre-tilting angle will It is desirable.Preferred materials here can produce than hitherto known material more for identical time of exposure during being polymerized Low pre-tilting angle, even if and/or can be with known materials by using it can also realize after shorter time of exposure (higher) pre-tilt angle obtained.Thus, production time (" pitch time ") of display can shorten and production technology Cost reduces.

Another problem of production PSA display is existence or the removal of the unpolymerized RM of residual volume, is particularly being used for After producing the polymerization procedure of pre-tilt angle in the display.Such as, this kind of not reacted RM such as may be existed by them Display is polymerized in uncontrollable mode during operation after making and negatively affects the character of display.

Therefore, PSA display known in the art often demonstrates what is called " image viscous (image sticking) " Or undesirable effect of " image burns ", the image produced by the of short duration addressing of single pixel the most in a liquid crystal display Remain visible after even the electric field in these pixels has been off or after other address pixels.

If used, there is the liquid crystal host mixture of low VHR, then on the one hand it may happen that " image viscous ".Daylight or the back of the body The UV-composition of scape illumination may cause liquid crystal molecule decomposition reaction undesirably and thus initiation ion or free radical wherein The generation of impurity.These may particularly be enriched with on electrode or oriented layer, and reduces the voltage effectively applied there.Should Effect also can be observed in the conventional LCD device do not have polymers compositions.

Additionally, due to there is extra " image viscous " effect often sight in PSA display that unpolymerized RM causes Observe.Uncontrolled being aggregated in of remaining RM causes here by the UV light from environment or background illumination.Therefore connecting Viewing area in, after multiple addressing periods, inclination angle changes.As a result, in the region connected, occur that transmission changes, And it keeps constant in the region of access failure.

Therefore, it is desirable that, the polymerization at PSA display production period RM is carried out and as far as possible the most completely Get rid of the existence of the most unpolymerized RM or be reduced to minima.For this reason, it may be necessary to can realize as far as possible effectively and The material being polymerized completely.Further, it is expected that the controlled reaction of these residual volumes.If RM is than hitherto known material faster And be more effectively polymerized, then this will be simpler.

Also exist to PSA display (particularly VA and OCB type) and for such display the most always In liquid crystal media and the biggest demand of polymerizable compound, they do not demonstrate shortcoming as above or only with the least Degree demonstrate these shortcomings and there is the character of improvement.Additionally, for PSA display and for the material of PSA display Material also exists the biggest demand, and it has favourable character, and particularly it is capable of while big operating temperature range having Even if high specific resistance short response time at low temperatures and low threshold voltage, low pre-tilt angle, substantial amounts of gray scale, high contrast Degree and wide visual angle, and there is " voltage keeps ratio " (VHR) and low-temperature stability of high numerical value after uv exposure, also referred to as " LTS ", i.e. liquid crystal compound are for the stability of the spontaneous crystallization of single component.

Summary of the invention

The task that the present invention is based on is, it is provided that for the novel applicable material of PSA display, particularly RM and bag Containing its liquid crystal media, it does not have defect as above or has these defects with the least degree, fast as far as possible and Fully it is polymerized, low pre-tilt angle can be regulated as quickly as possible, reduce or prevent that " image viscous " and excellent occurs in display Choosing can realize the highest ratio resistance value, low threshold voltage and short response time simultaneously.Additionally, liquid crystal media should have favorably Liquid crystalline phase character and high VHR and LTS value.

The further task of the present invention is to provide novel RM, especially for optics, electrooptics and electronic application with And proper method and the intermediate for preparing it is provided.

Particularly, the task that the present invention is based on produces bigger maximum pre-tilt angle after being to provide for photopolymerization Polymerizable compound, this causes realizing desired pre-tilt angle quickly and thus causing notable in production of liquid crystal displays The time shortened.

This task is passed through to provide material, method and liquid crystal display as described in the present application to realize according to the present invention.Especially Surprisingly, it was found that task as above can partly or entirely realize, its mode be by providing containing a kind of or The PSA display of the compound of the multiple polymerization bright according to we, or comprise one or more according to the present invention by use The liquid crystal media of polymerizable compound be used for producing this PSA display.Polymerizable compound according to the present invention contains work For mesomorphic group by the most mono-substituted terphenyl of halogen atom, and one or more polymerizable groups.Particularly preferably Be according to the present invention containing two or the compound of more than two polymerizable groups, wherein in these polymerizable groups At least one is connected on terphenyl group by spacer groups, and at least one in these polymerizable groups is directly connected to On terphenyl group, the most obstructed super-interval group.

This kind of polymerizable compound is used to cause in the liquid crystal media according to the present invention and PSA display desired pre- The fastest the realizing and cause the time significantly shortened at display production period in inclination angle.This can about liquid crystal media VA-inclining test box is verified by means of the pre-tilt measurement relying on time of exposure.Particularly, it is being added without light trigger In the case of can reach pre-tilt angle.

Owing to the polymerizable compound according to the present invention demonstrates significantly higher rate of polymerization, institute in PSA display Remain in liquid crystal cell with less unreacted residual volume, thus improve the controlled of its electrooptics character and these residual volumes Reaction becomes simpler.

Prior art has been described with polymerizable terphenyl compounds.WO2009/030329A1 discloses containing RM's PSA display, wherein RM only contains only a spacer groups and can also contain terphenyl group, but basis not explicitly disclosed The reactive terphenyl with lateral halogen substiuted of the present invention.WO93/22397A1 and US5,723,066 discloses has side To the terphenyl-RM of substituted two reactivities of fluorine, and containing in optically isotropic and transparent polymeric matrix The PDLC-display of separated microdroplet of liquid crystal compound, but not explicitly disclosed only contain only one according to the present invention The reactive terphenyl of spacer groups, or reactive terphenyl general service in PSA display.

Therefore, pass through the most former in PSA display according to the terphenyl of the reactive halogen substiuted of the present invention Position is polymerized and the special-purpose at fast setting inclination angle, does not the most describe, the most non-obvious.

It addition, have been found that the most surprisingly when for PSA display, only have one according to the present invention Individual spacer groups and the polymerizable compound by halogen the most mono-substituted mesomorphic terphenyl group, similar the having not than structure The polymerizable compound of substituted mesomorphic terphenyl group demonstrates that the inclination angle dramatically speeded up produces and dramatically speeds up and more complete Polymerization.This can be proved by direct contrast test.This result does not the most describe, the most aobvious and easy See.

Thus, the present invention relates to polymerizable compound in liquid crystal (FK) medium and PS or PSA (polymer-stabilized alignment) class Purposes in the liquid crystal display of type, described polymerizable compound contains by halogen atom, preferably the most mono-substituted by F or Cl Terphenyl group and one or more, preferably two or the polymerizable groups of more than two, the most preferably these polymerizables At least one in group is by directly (the most obstructed super-interval of at least one in spacer groups and these polymerizable groups Group) it is connected on terphenyl group (hereinafter also referred to " according to the polymerizable compound of the present invention ").

Moreover, it relates to liquid crystal media, its comprise one or more according to the polymerizable compound of the present invention and One or more can be mesomorphic, liquid crystal and/or polymerisable other compound.

Moreover, it relates to liquid crystal media, it comprises and is gathered according to the polymerizable compound of the present invention by one or more Close and the polymer that obtains, and one or more can be mesomorphic, liquid crystal and/or polymerisable other compound.

Moreover, it relates to liquid crystal media, it comprises

-polymerizable components A), it comprises one or more polymerizable compounds according to the present invention, and

-liquid crystal components B), hereinafter also referred to " liquid crystal host mixture ", its comprise one or more, preferably two kinds or more Multiple low-molecular-weight (monomer and the most polymerisable) compound the most hereinafter described.

The invention still further relates to the method for preparation liquid crystal media the most hereinafter described, wherein by the most hereinafter described One or more combinations of low molecular weight liquid crystals compounds or liquid crystal host mixture with one or more according to the polymerizable of the present invention Compound, and optionally mix with further liquid-crystal compounds and/or additive.

The present invention additionally relates to the polymerizable compound according to the present invention and according to the liquid crystal media of the present invention at PS and PSA Purposes in display, the particularly purposes in PS and the PSA display containing liquid crystal media, for by according to the present invention Polymerizable compound in PSA display situ polymerization and in liquid crystal media produce inclination angle, preferably apply electric field or In the case of magnetic field.

The invention still further relates to containing one or more polymerizable compounds according to the present invention or the liquid according to the present invention The liquid crystal display of crystalline medium, particularly PS or PSA display, particularly preferred PSA-VA, PSA-OCB, PSA-IPS, PSA- FFS, PSA-positivity-VA or PSA-TN display.

The invention additionally relates to the liquid crystal display of PS or PSA type, described display contains and has two substrates And the liquid crystal of the layer of the liquid crystal media of two electrodes and the component comprising polymerization between substrate and lower-molecular-weight component Box, at least one of which substrate is that light is permeable and at least one substrate has one or two electrode, wherein said poly- The component closed can obtain by being polymerized one or more polymerizable compounds in liquid crystal media between the substrate of liquid crystal cell, Preferably in the case of applying voltage to electrode, at least one of which polymerizable compound is selected from the polymerizable according to the present invention Compound.

The invention additionally relates to the production method of liquid crystal display the most hereinafter described, wherein will comprise such as context institute One or more the combinations of low molecular weight liquid crystals compounds stated or liquid crystal host mixture and one or more are according to the present invention's The liquid crystal media of polymerizable compound, is packed in the liquid crystal cell with two substrates and two electrodes the most hereinafter described Go, and this polymerizable compound is polymerized, be preferably polymerized in the case of applying voltage to electrode.

PS and PSA display according to the present invention has two electrodes of preferably form with clear layer, is wherein executed Be added to formed liquid crystal cell substrate one or two on.Here, or respectively an electrode is put on the every of two substrates On one, such as in PSA-VA, PSA-OCB or PSA-TN display according to the present invention, or by two electrodes Be applied only in two substrates, and another substrate do not have electrode, such as the PSA-positivity according to the present invention- In VA, PSA-IPS or PSA-FFS display like that.

Moreover, it relates to according to the novel polymerizable compound of the present invention, its preparation method and in these methods Use or thus obtained novel intermediate.

In context, applicable following implication:

Term " tilts " and " inclination angle " to refer to the liquid crystal molecule of liquid crystal media (the most excellent relative at liquid crystal display Select PS or PSA display) in the tilting or oblique orientation of surface of box.Inclination angle here represents the molecule at liquid crystal molecule Average angle between the longitudinal axis (liquid crystal director) and the surface of the parallel gripper shoe of plane that forms liquid crystal cell (< 90 °).Low number The inclination angle (deviating from the most greatly 90 ° of angles) of value is corresponding to big inclination.Suitably incline measurement method is given in an embodiment Go out.Except as otherwise noted, the inclination angle numerical value disclosed in context relates to this measuring method.

Term " mesomorphic group " is well known by persons skilled in the art and is described in the literature, and represents such base Group, it substantially contributes at lower-molecular substance or polymeric material due to its attraction and the anisotropy of the interaction of repulsion In cause liquid crystal (FK) phase.Compound (mesomorphic compound) containing mesomorphic group not necessarily itself must have liquid crystalline phase. Mesomorphic compound only shows that Mesomorphic behavior is also feasible after mixing with other compound and/or after being polymerized.Typical case Mesomorphic group be the little bar-shaped of such as rigidity or patelliform unit.Pure Appl.Chem.73 (5), 888 (2001) and C.Tschierske, G.Pelzl, S.Diele., Angew.Chem.2004,116,6340-6368 give relevant mesomorphic or The summary of the term and definition that liquid-crystal compounds is used.

Term " interval base " (English " spacer " or " spacer group "), is ability in context also referred to as " Sp " Field technique personnel are known and are described in the literature, for example, see Pure Appl.Chem.73 (5), 888 (2001) and C.Tschierske,G.Pelzl,S.Diele.,Angew.Chem.2004,116,6340-6368.Unless the contrary indicated otherwise, art Language " spacer groups " or " interval base " represent in polymerizable mesomorphic compound within a context by mesomorphic group and polymerizable group The flexible group that group is connected with each other.

Term " reactive mesogen " or " RM " represent containing mesomorphic group and one or more are suitable to the functional group of polymerization (also Be referred to as polymerizable groups or group P) compound.

Term " low molecular weight compound " and " not polymerizable compound " represent, do not contain and are suitable to those skilled in the art Under known normal condition, particularly functional group and typically monomer the chemical combination of polymerization under conditions of being polymerized for RM Thing.

" halogen " represents F, Cl, Br or I.

It is particularly preferably those of Formulas I according to the compound of the present invention:

Wherein each group has a following meanings:

P^a,P^bEach represent polymerizable groups independently of one another,

When Sp occurs every time identical or differently represent spacer groups,

L¹,L²,L³Represent F or Cl, group L the most independently of one another¹、L²And L³In one or more also illustrate that have 1, The alkyl being completely or partially fluorinated of 2 or 3 carbon atoms or alkoxyl, P^aOr P^a-Sp-, wherein group L¹、L²And L³In At least one represents F or Cl, preferably F,

R1, r2, r3 represent 0,1,2,3 or 4 the most independently of one another, wherein r1+r2+r3 >=1,

S1, s2 represent 0 or 1 the most independently of one another.

Polymerizable groups P^a,bIt is suitable for the reaction of the group of polyreaction, such as free radical or ionic chain polymerisation, addition polymerization Or polycondensation, or be suitable to polymeranaloguous reaction, such as in addition or condensation to main polymer chain.The suitableeest In the group of chain polymerization, especially with those of C=C double bond or-C ≡ C-tri-key, and be suitable to the base of ring-opening polymerisation Group, such as oxetanes (Oxetan) group or epoxide group.

Preferably group P^a,bSelected from CH₂=CW¹-CO-O-、CH₂=CW¹-CO-、 CH₂=CW²-(O)_k3-、CW¹=CH- CO-(O)_k3-、CW¹=CH-CO-NH-、CH₂=CW¹-CO-NH-、CH₃-CH=CH-O-、(CH₂=CH)₂CH-OCO-、(CH₂=CH- CH₂)₂CH-OCO-、(CH₂=CH)₂CH-O-、(CH₂=CH-CH₂)₂N-、(CH₂=CH-CH₂)₂N-CO-、HO-CW²W³-、HS- CW²W³-、HW²N-、HO-CW²W³-NH-、CH₂=CW¹-CO-NH-、CH₂=CH-(COO)_k1-Phe-(O)_k2-、CH₂=CH-(CO)_k1- Phe-(O)_k2-, Phe-CH=CH-, HOOC-, OCN-and W⁴W⁵W⁶Si-, wherein W¹Represent H, F, Cl, CN, CF₃, phenyl or have 1 To the alkyl of 5 C atoms, particularly H, F, Cl or CH₃, W²And W³Represent H the most independently of each other or there is 1 to 5 C atom Alkyl, particularly H, methyl, ethyl or n-pro-pyl, W⁴、W⁵And W⁶Represent Cl the most independently of each other, there is 1 to 5 C atom Oxa alkyl or oxa-carbonylic alkyl, W⁷And W⁸Represent H, Cl the most independently of each other or there is the alkyl of 1 to 5 C atom, Phe represents Isosorbide-5-Nitrae-phenylene, and it is optionally replaced by one or more group L being different from P-Sp-as defined above, k₁、k₂ And k₃Represent 0 or 1, k the most independently of each other₃Preferably represent 1, and k₄Represent the integer from 1 to 10.

Particularly preferred group P^a,bSelected from CH₂=CW¹-CO-O-、CH₂=CW¹-CO-、

CH₂=CW²-O-、CW¹=CH-CO-(O)_k3-、CW¹=CH-CO-NH-、CH₂=CW¹-CO-NH-、(CH₂=CH)₂CH- OCO-、(CH₂=CH-CH₂)₂CH-OCO-、(CH₂=CH)₂CH-O-、(CH₂=CH-CH₂)₂N-、(CH₂=CH-CH₂)₂N-CO-、CH₂= CW¹-CO-NH-、CH₂=CH-(COO)_k1-Phe-(O)_k2-、CH₂=CH-(CO)_k1-Phe-(O)_k2-, Phe-CH=CH-and W⁴W⁵W⁶Si-, wherein W¹Represent H, F, Cl, CN, CF₃, phenyl or there is the alkyl of 1 to 5 C atoms, particularly H, F, Cl or CH₃, W²And W³Represent H the most independently of one another or there is the alkyl of 1 to 5 C atoms, particularly H, methyl, ethyl or positive third Base, W⁴、W⁵And W⁶Each represent Cl, the oxa alkyl with 1 to 5 C atoms or oxa-carbonylic alkyl, W independently of one another⁷And W⁸ Each representing H, Cl independently of one another or have the alkyl of 1 to 5 C atoms, Phe represents Isosorbide-5-Nitrae-phenylene, k₁、k₂And k₃Each Represent 0 or 1, k independently of one another₃Preferably represent 1 and k₄Represent the integer from 1 to 10.

Highly preferred group P^a,bSelected from CH₂=CW¹-CO-O-, particularly CH₂=CH-CO-O-、CH₂=C(CH₃)-CO-O- And CH₂=CF-CO-O-, also CH₂=CH-O-、(CH₂=CH)₂CH-O-CO-、(CH₂=CH)₂CH-O-、With

Other particularly preferred group P^a,bSelected from vinyl oxygen, acrylate, methacrylate, fluoro acrylic ester, Chloropropene acid esters, oxetanes and epoxide group, particularly preferably represent acrylate or methacrylic acid ester group.

Preferably interval base Sp is selected from formula Sp''-X'' so that group " P^a/b-Sp-" corresponding to formula " P^a/b-Sp''- X''-", wherein

Sp'' represent have 1～20, the alkylidene of preferably 1～12 carbon atom, it is optionally by F, Cl, Br, I or CN Single-or polysubstituted, and wherein one or more non-conterminous CH₂Group extraly can the most independently of one another by-O-,- S-、-NH-、-N(R⁰)-、-Si(R⁰⁰R⁰⁰⁰)-、-CO-、-CO-O-、-O-CO-、-O-CO-O-、-S-CO-、-CO-S-、-N(R⁰⁰)- CO-O-、-O-CO-N(R⁰⁰)-、-N(R⁰⁰)-CO-N(R⁰⁰)-,-CH=CH-or-C ≡ C-so that O-and/or S-atom not that This mode being directly bonded to replaces,

X'' represents-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-,-CO-N (R⁰⁰)-、-N(R⁰⁰)-CO-、-N (R⁰⁰)-CO-N(R⁰⁰)-、-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、- CF₂CH₂-、-CH₂CF₂-、-CF₂CF₂-、-CH=N-、-N=CH-、-N=N-、-CH=CR⁰-、-CY²=CY³-、-C≡C-、-CH=CH- CO-O-,-O-CO-CH=CH-or singly-bound,

R⁰⁰And R⁰⁰⁰Represent H the most independently of each other or there is the alkyl of 1 to 12 carbon atom, and

Y²And Y³Represent H, F, Cl or CN the most independently of each other.

X' preferably-O-,-S-,-CO-,-COO-,-OCO-,-O-COO-,-CO-NR⁰-、-NR⁰-CO-、-NR⁰-CO- NR⁰-or singly-bound.

Typical interval base Sp'' is such as-(CH₂)_p1-、-(CH₂CH₂O)_q1-CH₂CH₂-、-CH₂CH₂-S-CH₂CH₂-、- CH₂CH₂-NH-CH₂CH₂-or-(SiR⁰⁰R⁰⁰⁰-O)_p1-, wherein p1 is the integer of 1 to 12, and q1 is the integer of 1 to 3, and R⁰⁰With R⁰⁰⁰There is implication given above.

Particularly preferred group-Sp''-X''-is-(CH₂)_p1-、-(CH₂)_p1-O-、-(CH₂)_p1-O-CO-、-(CH₂)_p1- O-CO-O-, wherein p1 and q1 has implication as above.

Particularly preferred group Sp'' such as, under every kind of situation be the ethylidene of straight chain, propylidene, butylidene, pentylidene, Hexylidene, heptamethylene, octylene, nonamethylene, decylene, alkylene undecyl, sub-dodecyl, alkylene octadecyl, ethylidene oxygen Base ethylidene, methyleneoxybutylene, ethylidene sulfur are for ethylidene, ethylene-N-methyl imino group ethylidene, 1-methyl Asia Alkyl, ethenylidene, allylidene and butenylidene.

In another preferred implementation of the present invention, the P in Formulas I^aAnd/or P^bRepresent that there is two or more polymerizables The group (multifunctional polymerizable groups) of group.Such suitable groups, and containing they polymerizable compound and It is prepared, and is described in such as US7, in 060,200B1 or US2006/0172090A1.Particularly preferably can selected from the multifunctional of following formula Polymeric residues:

-X-alkyl-CHP¹-CH₂-CH₂P² l*a

-X-alkyl-C(CH₂P¹)(CH₂P²)-CH₂P³ l*b

-X-alkyl-CHP¹CHP²-CH₂P³ l*c

-X-alkyl-C(CH₂P¹)(CH₂P²)-C_aaH_2aa+1 l*d

-X-alkyl-CHP¹-CH₂P² l*e

-X-alkyl-CHP^lP² l*f

-X-alkyl-CP¹P²-C_aaH_2aa+1 l*g

-x-alkyl-C(CH₂p¹)(CH₂p²)-CH₂OCH₂-C(CH₂p³)(CH₂P⁴)CH₂P⁵ l*h

-X-alkyl-CH((CH₂)_aaP¹)((CH₂)_bbP²) l*i

-X-alkyl-CHP¹CHP²-C_aaH_2aa+1 1*k

-X'-alkyl-C(CH₃)(CH₂P¹)(CH₂P²) l*m

Wherein

Alkyl represents singly-bound or the straight chain with 1～12 carbon atom or branched alkylidene, wherein one or more Non-conterminous CH₂Group can also be the most independently of one another by-C (R⁰⁰)=C(R⁰⁰⁰)-、-C≡C-、-N(R⁰⁰)-、-O-、-S-、- CO-,-CO-O-,-O-CO-,-O-CO-O-are so that the mode of O and/or S atom keyed jointing the most directly with one another replaces, and wherein One or more H atom can also be replaced by F, Cl or CN, wherein R⁰⁰And R⁰⁰⁰There is implication as above.

Aa and bb represents 0,1,2,3,4,5 or 6 the most independently of one another,

X has for one of implication given by X', and

P^1-5Each have independently of one another for P^aOne of given implication.

In the formula of context,

Preferably represent

Or

When wherein L occurs every time, there is the one of the implication shown in context identical or differently, and preferably represent F, Cl、CN、NO₂、CH₃、C₂H₅、C(CH₃)₃、CH(CH₃)₂、CH₂CH(CH₃)C₂H₅、OCH₃、OC₂H₅、COCH₃、COC₂H₅、COOCH₃、 COOC₂H₅、CF₃、OCF₃、OCHF₂、OC₂F₅Or P-Sp-, particularly preferred F, Cl, CN, CH₃、C₂H₅、OCH₃、COCH₃、OCF₃Or Person P-Sp-, highly preferred F, Cl, CH₃、OCH₃、COCH₃Or OCF₃。

The compound of the minor shown in particularly preferred Formulas I and context thereof is more such, wherein:

-L¹、L²And L³It not P^a-(Sp)_s1-and P^b-(Sp)_s2-,

-one or more, preferably all of L¹、L²And L³Represent F and/or Cl, particularly preferred F,

-r1+r2+r3's and be 1,2,3 or 4,

One or two in-r1, r2 and r3 represents 0,

-r2 represents 1 or 2,

-r1 and/or r3 represents 1,

-s1 and s2 each represents 0,

-s1 and s2 each represents 1,

-s1 represents that 1 and s2 represents 0, or s1 represents that 0 and s2 represents 1,

Another in-parameter s1 and s2 one expression 0 and parameter s1 and s2 represents 1.

The compound of extremely preferred Formulas I is selected from following minor:

Wherein P^a、P^b、S_pWith s1, there is one of implication shown in context, and s1 is preferably 1.

Pa and P in the compound of Formulas I and minor thereof^bPreferably represent acrylate or methacrylate, and also have Fluorinated acrylic ester.

In the compound of Formulas I and minor thereof, Sp preferably represents-(CH₂)_p1-、-(CH₂)_p1-O-、-(CH₂)_p1-O-CO-or Person-(CH₂)_p1-O-CO-O-, wherein p1 represents the integer from 1 to 12, preferably 1 to 6, particularly preferred 1,2 or 3, wherein these bases Roll into a ball in the way of O atom not direct neighbor and P^aOr P^bConnect.

The invention further relates to the new compound of Formulas I the most as defined below and minor thereof, wherein s1 and s2 is not Represent 1 simultaneously.

The invention still further relates to the new intermediate of the compound for formula I, it is selected from formula II

Wherein Sp, L¹、L²、L³, r1, r2, r3, s1 and s2 there is the implication in Formulas I or shown in context, wherein s1 and Both do not represent 1 to s2 simultaneously, and G and G' represents H atom or blocking group the most independently of one another.

Suitably protection group G is known to a person skilled in the art.Preferably protection group is alkyl, acyl group and alkyl Silicyl or arylsilyl groups, 2-THP trtrahydropyranyl or methoxy.

The intermediate of particularly preferred formula II is selected from above-mentioned minor I1-I9 mentioned, wherein P^aG-is represented in the case of every kind O-and P^bExpression-O-G' in the case of every kind, wherein G and G' preferably represents H.

In presently preferred embodiment, according to spacer groups in the polymerizable compound of the present invention not Containing C-C tri-key (-C ≡ C-), or as described above Formulas I and II and minor in Sp and Sp'' without C-C tri-key (-C ≡ C-)。

For formula I and II and the compound of its minor and the most suitable and preferred method of intermediate, such as It is shown below in schematic diagram, and preferably includes one or more steps as described below.

Formulas I and II and the compound of its minor and middle physical ability are by known with technical staff and be described in organic chemistry Standard reading matter in method be similarly prepared, such as at Houben-Weyl, Methoden der organischen Chemie [organic chemistry procedures], in Thieme-Verlag, Stuttgart.

Such as, the synthesis of the compound of Formulas I comprises corresponding acid, acid derivative or the halo chemical combination of group P by employing The intermediate of thing esterification or etherificate Formula II is carried out.Such as shown in schematic diagram 1 (wherein R represents H or CH₃), wherein Pa and P^bRepresent the compound of the Formulas I of acrylate or methacrylic acid ester group, can be by using acid derivative such as (first Base) acryloyl chloride or (methyl) acrylic anhydride at alkali and be optionally esterified in the presence of 4-(N, N-dimethylamino) pyridine (DMAP) The alcohol of the corresponding wherein Formula II of G=G'=H obtains.Additionally, this alcohol can also use (methyl) acrylic acid to exist at dehydrant Under esterified, such as according to use dicyclohexylcarbodiimide (DCC) Steglich method.

Schematic diagram 1

(R=H or CH₃, " (Sp) "=Sp or singly-bound)

The intermediate of Formula II is such as by transition metal-catalyzed halogenated aryl hydrocarbon (Hal=Cl, Br, I, OTf) and metal aryl The cross-coupling (seeing schematic diagram 2) of compound synthesizes, such as by Suzuki coupling (M=B (OH)₂, B (OR)₂)、 Negishi coupling (M=ZnHal) or Kumada coupling (M=MgHal).

Schematic diagram 2

Here, aryle itself can be obtained by halogenated aryl hydrocarbon, or directly by obtaining lattice with reactive magnesium Family name's compound, or by using the halogen-lithium of butyl lithium to exchange and using zinc salt or the trans-metallation of magnesium salt subsequently (Transmetallierung).Lithium compound obtains borate with the reaction of trialkylborates, can be by it by hydrolyzing To free boric acid.

Biphenyl composite structure unit described in schematic diagram 2 can similarly prepare (schematic diagram 3), wherein passes through Dihalogenated aromatic compounds and aryle is made to react in cross-coupling reaction.Here substituent group Hal and Hal' can With identical or different.

Schematic diagram 3

In order to prepare PSA display, under applying voltage condition, polymerizable compound is the substrate of liquid crystal display Between liquid crystal media in be polymerized by in-situ polymerization or cross-link (if a kind of compound comprises two or more polymerizable group Group).Polymerization can be carried out in one step.Can also carry out being polymerized with shape the most in the first step under applying voltage condition Become pre-tilt angle, be then polymerized under not applying voltage condition in the second polymerization procedure or cross-link the most anti- The compound (" final solidification (end curing) ") that should fall.

Suitable and preferred polymerization is, such as, and heat or photopolymerization, preferably photopolymerization, particularly UV photopolymerization.At this Can also optionally add one or more initiators.Suitable polymerizing condition and suitable initiator type and consumption are these Known to the skilled person and be described in the literature.Being suitable to radical polymerization, such as, commercially available is light-initiated AgentIrgacureIrgacureIrgacureOr Darocure(Ciba AG).If use initiator, its ratio is preferably 0.001～5 weight %, particularly preferred 0.001～1 weight Amount %.

Polymerizable compound according to the present invention is also suitably for the polymerization not having initiator, this results in significant advantage, example Such as relatively low material cost and the most less liquid crystal caused by initiator or its catabolite of possible surplus Medium pollution.Therefore, polymerization can also be carried out in the case of being added without initiator.Therefore at one preferred embodiment In, liquid crystal media does not comprise polymerization initiator.

Polymerizable components A) or liquid crystal media can also comprise one or more stabilizers, to prevent less desirable RM spontaneous Polymerization, such as, storing or during transport.The proper types of stabilizer and consumption are to well known to a person skilled in the art and at literary composition It is described in offering.Particularly suitable, such as, commercially availableSeries (Ciba AG) stabilizer, such as1076.If use stabilizer, then based on RM or polymerizable components A) total amount meter, their ratio is preferred It is 10～10,000ppm, particularly preferably 50～500ppm.

The liquid crystal media according to the present invention for PSA display preferably comprise < 5 weight %, particularly preferably < 1 weight %, non- The most particularly preferably < the polymerizable compound of the polymerizable compound of 0.5 weight %, Formulas I the most mentioned above and its minor.

Particularly preferably comprise one, two or three according to the liquid crystal media of the polymerizable compound of the present invention.

It is then preferred that such liquid crystal media, wherein polymerizable components (component A) only comprises gathering according to the present invention Polymerisable compounds.

It is then preferred that such liquid crystal media, wherein component B) it is liquid-crystal compounds or the liquid crystal with Nematic liquid crystalline phase Mixture.

Further preferably according to the achiral polymerisable compound of the present invention and wherein component A) and/or compound B) only select From the liquid crystal media of non-chiral compound.

It is then preferred that such liquid crystal media, wherein polymerizable components or component A) comprise one or more according to the present invention The polymerizable compound with a polymerizable groups (single reaction) and one or more according to the present invention, there are two Or more, the polymerizable compound of preferably two polymerizable groups (two or multiple reactionness).

It is then preferred that such PSA display and liquid crystal media, wherein polymerizable components or component A) only comprise according to this The polymerizable compound with two polymerizable groups (two is reactive) of invention.

Polymerizable components or component A) according to the ratio in the liquid crystal media of the present invention preferably < 5%, particularly preferably < 1%, Very particularly preferably < 0.5%.

Liquid crystal components or component B) preferred according to the ratio in the liquid crystal media of the present invention > 95%, particularly preferably > 99%.

Polymerizable compound according to the present invention can each auto polymerization but it also may polymerization comprises two or more bases The mixture of the polymerizable compound of the present invention, or polymerization comprise one or more according to the polymerizable compound of the present invention with One or more are preferably the mixture of other polymerizable compounds (comonomer) of mesomorphic or liquid crystal.Such mixed in polymerization During compound, form copolymer.The invention still further relates to polymerizable mixture the most hereinafter described.This polymerizable compound and copolymerization Monomer is mesomorphic or non-mesogenic, preferably mesomorphic or liquid crystal.

Suitably and preferably, the mesogenic comonomers compound selected from such as following formula of PSA display it is particularly useful for:

Wherein, each group has a following meanings:

P¹And P²Each represent polymerizable groups independently of one another, preferably have as above below with the implication described in P it One, particularly preferred acrylate, methacrylate, fluorinated acrylic ester, oxetanes, vinyl epoxide or epoxy radicals Group,

Sp¹And Sp²Represent singly-bound or spacer groups the most independently of one another, preferably have as above below with described in Sp One of implication, and particularly preferably expression-(CH₂)_p1-、-(CH₂)_p1-O-、-(CH₂)_p1-CO-O-or-(CH₂)_p1-O-CO-O-, Wherein p1 be from 1 to 12 integer and wherein the group finally mentioned with adjacent ring connect through O atom realize,

Wherein group P¹-Sp¹-and P²-Sp²-one or more can represent R^aa, condition is the group P existed¹-Sp¹- And P²-Sp²-at least one do not indicate that R^aa,

R^aaRepresent H, F, Cl, CN or there is the straight or branched alkyl of 1 to 25 carbon atoms, the most one or more Non-conterminous CH₂Group can be independently of one another by C (R⁰)=C(R⁰⁰)-、-C≡C-、-N(R⁰)-、-O-、-S-、-CO-、-CO-O-、- O-CO-,-O-CO-O-so that O and/or S atom directly the most each other the mode of keyed jointing replace, and one or many most in addition Individual H atom can be by F, Cl, CN or P¹-Sp¹-replace, particularly preferably have 1 to 12 carbon atoms straight chain or branched, optional single or Polyfluorizated alkyl, alkoxyl, thiazolinyl, alkynyl, alkyl-carbonyl, alkoxy carbonyl, alkyl-carbonyl epoxide or alkoxy carbonyl oxygen Base (wherein thiazolinyl and alkynyl there is at least two carbon atom and branched groups has at least three carbon atom),

R⁰,R⁰⁰When each independently of one another and occurring every time identical or differently represent H or there are 1 to 12 carbon atoms Alkyl,

R^yAnd R^zEach represent H, F, CH independently of one another₃Or CF₃,

Z¹Represent-O-,-CO-,-C (R^yR^z)-or-CF₂CF₂-,

Z²And Z³Represent-CO-O-,-O-CO-,-CH the most independently of one another₂O-、-OCH₂-、-CF₂O-、-OCF₂-or- (CH₂)_n-, wherein n is 2,3 or 4,

When L occurs every time identical or differently represent F, Cl, CN have 1 to 12 carbon atoms straight chain or branched, The alkyl of optional single or multiple fluorination, alkoxyl, thiazolinyl, alkynyl, alkyl-carbonyl, alkoxy carbonyl group, alkyl-carbonyl epoxide or alkoxyl Carbonyl epoxide, preferably F,

L' and L'' represents H, F or Cl the most independently of one another,

R represents 0,1,2,3 or 4,

S represents 0,1,2 or 3,

T represents 0,1 or 2,

X represents 0 or 1.

In the compound of formula M1 to M29,

Preferably represent

Or

When wherein L occurs every time identical or differently there is one of implication shown in context, and preferably represent F, Cl, CN、NO₂、CH₃、C₂H₅、C(CH₃)₃、CH(CH₃)₂、CH₂CH(CH₃)C₂H₅、OCH₃、OC₂H₅、COCH₃、COC₂H₅、COOCH₃、 COOC₂H₅、CF₃、OCF₃、OCHF₂、OC₂F₅Or P-Sp-, particularly preferred F, Cl, CN, CH₃、C₂H₅、OCH₃、COCH₃、OCF₃Or Person P-Sp-, highly preferred F, Cl, CH₃、OCH₃、COCH₃Or OCF₃, particularly F or CH₃。

In addition to above-mentioned polymerizable compound, the liquid crystal media for the liquid crystal display according to the present invention includes liquid crystal Mixture (" body mixture "), its contain one or more, preferred two or more low-molecular-weights (i.e. monomer or unpolymerized ) compound.The latter is stable or anergy for polyreaction under conditions of being polymerized for polymerizable compound. In principle, the arbitrary liquid crystal compound being suitable for tradition VA and OCB display is suitable as body mixture.Suitable liquid Brilliant mixture is to well known to a person skilled in the art and be described in the literature, the such as VA display in EP1378557A1 In mixture, and the mixture for OCB display in EP1306418A1 and DE10224046A1.

Referenced below particularly preferred liquid crystal display, liquid crystal host mixture and liquid crystal media:

First preferred embodiment in, liquid crystal media comprises based on the compound with negative dielectric anisotropy Liquid crystal host mixture.This liquid crystal media is particularly suitable for PSA-VA display.The liquid crystal media of the type is particularly preferred Embodiment is at following a)-x) partly mention:

A) liquid crystal media, it comprises the compound of one or more of formula CY and/or PY:

Wherein each group has a following meanings:

A represents 1 or 2,

B represents 0 or 1,

RepresentOr

R¹And R²Representing the alkyl with 1 to 12 carbon atom the most independently of each other, wherein one or two is non-conterminous CH₂Group can also be by-O-,-CH=CH-,-CO-,-OCO-or-COO-so that the mode of O atom direct keyed jointing the most each other Replace, preferably there is alkyl or the alkoxyl of 1 to 6 carbon atom,

Z^xAnd Z^yExpression-CH the most independently of each other₂CH₂-、-CH=CH-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-、- CO-O-、-O-CO-、-C₂F₄-、-CF=CF-、-CH=CH-CH₂O-or singly-bound, preferably singly-bound,

L^1-4Represent F, Cl, OCF the most independently of each other₃、CF₃、CH₃、CH₂F、CHF₂。

Preferred group L¹And L²Both represent F, or group L¹And L²An expression F and another represent Cl, or base Group L³And L⁴Both represent F, or group L³And L⁴One expression F and another represent Cl.

The compound of formula CY is preferably selected from following minor:

Wherein a represents 1 or 2, Alkyl and Alkyl* represents the straight chain alkane with 1 to 6 carbon atom the most independently of each other Base group, and Alkenyl represents the straight-chain alkenyl group with 2 to 6 carbon atoms, and (O) represents oxygen atom or singly-bound. Alkenyl preferably represents CH₂=CH-、CH₂=CHCH₂CH₂-、CH₃-CH=CH-、CH₃-CH₂-CH=CH-、CH₃-(CH₂)₂-CH= CH-、CH₃-(CH₂)₃-CH=CH-or CH₃-CH=CH-(CH₂)₂-。

The compound of formula PY is preferably selected from following minor:

Wherein Alkyl and Alkyl* represents the linear alkyl groups with 1 to 6 carbon atom the most independently of each other, and Alkenyl represents the straight-chain alkenyl group with 2 to 6 carbon atoms, and (O) represents oxygen atom or singly-bound.The preferred table of Alkenyl Show CH₂=CH-、CH₂=CHCH₂CH₂-、CH₃-CH=CH-、CH₃-CH₂-CH=CH-、CH₃-(CH₂)₂-CH=CH-、CH₃-(CH₂)₃-CH =CH-or CH₃-CH=CH-(CH₂)₂-。

B) liquid crystal media, it additionally comprises the compound of one or more of following formula:

Wherein each group has a following implication:

RepresentOr

RepresentOr

R³And R⁴Represent that there is the alkyl of 1 to 12 carbon atom the most independently of each other, in addition wherein one or two not phase Adjacent CH₂Group can also be by-O-,-CH=CH-,-CO-,-O-CO-or-CO-O-so that O atom keyed jointing the most each other Mode replace,

Z^yExpression-CH₂CH₂-、-CH=CH-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-、-CO-O-、-O-CO-、- C₂F₄-、-CF=CF-、-CH=CH-CH₂O-or singly-bound, preferably singly-bound.

The compound of formula ZK is preferably selected from the group of following minor:

Wherein Alkyl and Alkyl* represents the linear alkyl groups with 1 to 6 carbon atom the most independently of each other, and Alkenyl represents the straight-chain alkenyl group with 2 to 6 carbon atoms.Alkenyl preferably represents CH₂=CH-、CH₂= CHCH₂CH₂-、CH₃-CH=CH-、CH₃-CH₂-CH=CH-、CH₃-(CH₂)₂-CH=CH-、CH₃-(CH₂)₃-CH=CH-or CH₃-CH= CH-(CH₂)₂-。

C) liquid crystal media, it additionally comprises the compound of one or more of following formula:

Wherein, each group has following implication in the same manner or differently when occurring every time:

R⁵And R⁶Each have independently of one another as described above for R¹One of specified implication,

RepresentOr

RepresentOrWith

E represents 1 or 2.

The compound of formula DK is preferably selected from the group of following minor:

Wherein Alkyl and Alkyl* represents the linear alkyl groups with 1 to 6 carbon atom the most independently of each other, and Alkenyl Yu Alkenyl* represents the straight-chain alkenyl group with 2 to 6 carbon atoms the most independently of each other.Alkenyl with Alkenyl* preferably represents CH₂=CH-、CH₂=CHCH₂CH₂-、CH₃-CH=CH-、CH₃-CH₂-CH=CH-、CH₃-(CH₂)₂-CH= CH-、CH₃-(CH₂)₃-CH=CH-or CH₃-CH=CH-(CH₂)₂-。

D) liquid crystal media, it additionally comprises the compound of one or more of following formula:

Wherein each group has a following implication:

RepresentOr

F represents 0 or 1,

R¹And R²Representing the alkyl with 1 to 12 carbon atom the most independently of each other, wherein one or two is non-conterminous CH₂Group can also be by-O-,-CH=CH-,-CO-,-OCO-or-COO-so that the mode of O atom keyed jointing the most each other Replace,

Z^xAnd Z^yExpression-CH the most independently of each other₂CH₂-、-CH=CH-、-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂-、- CO-O-、-O-CO-、-C₂F₄-、-CF=CF-、-CH=CH-CH₂O-or singly-bound, preferably singly-bound,

L¹And L²Represent F, Cl, OCF the most independently of each other₃、CF₃、CH₃、CH₂F、CHF₂。

Preferably two group L¹And L²Represent F, or group L¹And L²One expression F and another represent Cl.

The compound of formula LY is preferably selected from the group of following minor:

Wherein R¹Having implication given above, Alkyl represents the straight chained alkyl with 1-6 carbon atom, and (O) represents oxygen Atom or singly-bound and v represent the integer of 1 to 6.R¹Preferably represent and there is the straight chained alkyl of 1 to 6 carbon atom or there are 2 to 6 The straight-chain alkenyl of carbon atom, particularly CH₃、C₂H₅、n-C₃H₇、n-C₄H₉、n-C₅H₁₁、CH₂=CH-、CH₂=CHCH₂CH₂-、CH₃-CH =CH-、CH₃-CH₂-CH=CH-、CH₃-(CH₂)₂-CH=CH-、CH₃-(CH₂)₃-CH=CH-or CH₃-CH=CH-(CH₂)₂-。

E) liquid crystal media, it additionally comprises the one or more of compound selected from following formula:

Wherein alkyl represents C_1-6Alkyl, L^xRepresent that H or F and X represents F, Cl, OCF₃、OCHF₂Or OCH=CF₂.The most excellent Selecting the compound of formula G1, wherein X represents F.

F) liquid crystal media, it additionally comprises the one or more of compound selected from following formula:

Wherein R⁵Have previously for R¹One of implication be given, alkyl represents C_1-6Alkyl, d represents 0 or 1, and z and m divides Represent the integer of 1 to 6 the most independently of each other.R⁵Particularly preferably C in these compounds_1-6-alkyl or-alkoxyl or C_2-6- Alkenyl, d is preferably 1.Liquid crystal media according to the present invention preferably comprises the compound of one or more of formula described above, its Amount >=5 weight %.

G) liquid crystal media, it additionally comprises the one or more of biphenol compound selected from following formula:

Wherein Alkyl and Alkyl* represents the linear alkyl groups with 1 to 6 carbon atom the most independently of each other, and Alkenyl and Alkenyl* represents the straight-chain alkenyl group with 2 to 6 carbon atoms the most independently of each other.Alkenyl and Alkenyl* preferably represents CH₂=CH-、CH₂=CHCH₂CH₂-、CH₃-CH=CH-、CH₃-CH₂-CH=CH-、CH₃-(CH₂)₂-CH= CH-、CH₃-(CH₂)₃-CH=CH-or CH₃-CH=CH-(CH₂)₂-。

The biphenyl of formula B1 to B3 ratio in liquid crystal compound is preferably at least 3 weight %, particularly >=5 weight %.

The compound of formula B2 is particularly preferred.

The compound of formula B1 to B3 is preferably selected from following minor:

Wherein Alkyl* represents the alkyl group with 1 to 6 carbon atom.Medium according to the present invention particularly preferably comprises One or more of formulas B1a and/or the compound of B2c.

H) liquid crystal media, it additionally comprises the terphenyl compounds of one or more of following formula:

Wherein R⁵And R⁶Have the most independently of each other above for R¹One of implication be given and

WithRepresent the most independently of each other:OrWherein L⁵Represent F or Cl, preferably F, and L⁶Represent F, Cl, OCF₃、CF₃、CH₃、CH₂F or CHF₂, preferably F.

The compound of formula T is preferably selected from following minor:

Wherein R represents straight chained alkyl or the alkoxyl with 1 to 7 carbon atom, and R* represents have 2 to 7 carbon atoms Straight-chain alkenyl, (O) represents oxygen atom or singly-bound, and m represents the integer of 1 to 6.R* preferably represents CH₂=CH-、CH₂= CHCH₂CH₂-、CH₃-CH=CH-、CH₃-CH₂-CH=CH-、CH₃-(CH₂)₂-CH=CH-、CH₃-(CH₂)₃-CH=CH-or CH₃-CH= CH-(CH₂)₂-。

R preferably represent methyl, ethyl, propyl group, butyl, amyl group, hexyl, methoxyl group, ethyoxyl, propoxyl group, butoxy or Amoxy.

Liquid crystal media according to the present invention preferably comprises formula T and the terphenyl of preferred minor thereof, and its amount is preferably 0.5-30 Weight %, particularly 1-20 weight %.

Formula T1, the compound of T2, T3 and T21 are particularly preferred.In these compounds, R preferably represents alkyl, also has Alkoxyl, is respectively provided with 1 to 5 carbon atom.

If the Δ n value of mixture answers >=0.1, in the mixture according to the present invention, the most preferably use terphenyl.Excellent The mixture of choosing comprises the terphenyl compounds of one or more formulas T of 2～20 weight %, be preferably chosen from compound T1～ T22。

I) liquid crystal media, it additionally comprises the compound of one or more of following formula:

Wherein R¹And R²There is implication given above, and represent that there is 1 to 6 carbon atom the most independently of each other Straight chained alkyl or there is the straight-chain alkenyl of 2 to 6 carbon atoms.

Preferably medium comprises one or more of selected from formula O1, the compound of O3 and O4.

K) liquid crystal media, it additionally comprises the compound of one or more of following formula:

Wherein

Represent

R⁹Represent H, CH₃、C₂H₅Or n-C₃H₇, (F) represents that optional fluoro substituents and q represent 1,2 or 3, and R⁷It is right to have In R¹One of implication be given, its content is preferably > 3 weight %, particularly >=5 weight %, and particularly it is preferably 5 to 30 weights Amount %.

The compound of particularly preferred formula FI is selected from following minor:

Wherein R⁷Preferably represent straight chained alkyl and R⁹Represent CH₃、C₂H₅Or n-C₃H₇.Formula FI1, the compound of FI2 and FI3 are Particularly preferred.

M) liquid crystal media, it additionally comprises the one or more of compound selected from following formula:

Wherein R⁸Have for R¹The implication be given and Alkyl represent the straight chained alkyl with 1 to 6 carbon atom.

N) liquid crystal media, it comprises one or more of compound extraly, and described compound has tetralyl unit Or naphthyl unit, it is selected from the compound of following formula:

Wherein R¹⁰And R¹¹Have the most independently of each other for R¹One of implication be given, preferably represents have 1 to 6 carbon The straight chained alkyl of atom or alkoxyl or there is the straight-chain alkenyl of 2 to 6 carbon atoms, and Z¹And Z²Table the most independently of each other Show-C₂H₄-、-CH=CH-、-(CH₂)₄-、-(CH₂)₃O-、-O(CH₂)₃-、-CH=CH-CH₂CH₂-、-CH₂CH₂CH=CH-、- CH₂O-、-OCH₂-、-CO-O-、-O-CO-、-C₂F₄-、-CF=CF-、-CF=CH-、-CH=CF-、-CH₂-or singly-bound.

O) liquid crystal media, it comprises two fluoro dibenzo chromane and/or chromanes of one or more of following formula extraly:

Wherein

R¹¹And R¹²There is implication given above the most independently of each other,

Ring M represents anti-form-1,4-cyclohexylidene or Isosorbide-5-Nitrae-phenylene,

Z^mExpression-C₂H₄-、-CH₂O-、-OCH₂-,-CO-O-or-O-CO-,

C represents 0 or 1,

Its amount is preferably 3 to 20 weight %, specifically for 3 to 15 weight %.

Particularly preferred formula BC, CR and RC compound selected from following minor:

Wherein Alkyl and Alkyl* represents the straight chained alkyl with 1 to 6 carbon atom the most independently of each other, and (O) represents Oxygen atom or singly-bound, c represents 1 or 2, and Alkenyl and Alkenyl* represents have 2 to 6 carbon the most independently of each other The straight-chain alkenyl of atom.Alkenyl and Alkenyl* preferably represents CH₂=CH-、CH₂=CHCH₂CH₂-、CH₃-CH=CH-、CH₃- CH₂-CH=CH-、CH₃-(CH₂)₂-CH=CH-、CH₃-(CH₂)₃-CH=CH-or CH₃-CH=CH-(CH₂)₂-。

Very particularly preferably be the mixture of the compound comprising one, two or three formula BC-2.

P) liquid crystal media, its phenanthrene of fluorination comprising one or more of following formula extraly and/or dibenzofurans:

Wherein R¹¹And R¹²There is implication given above the most independently of each other, b represent 0 or 1, L represent F and r represent 1, 2 or 3.

The compound of particularly preferred formula PH and BF is selected from following minor:

Wherein R and R' represents straight chained alkyl or the alkoxyl with 1 to 7 carbon atom the most independently of each other.

Q) liquid crystal media, its except the polymerizable compound according to the present invention, particularly Formulas I or its minor compound with And outside comonomer, do not comprise and there is terminal ethylenyl groups epoxide (-O-CH=CH₂) compound.

R) liquid crystal media, it comprises 1～5, preferably 1,2 or 3 kind of polymerizable compound, be preferably selected from according to the present invention can Polymerizable compound, particularly Formulas I or its minor.

S) ratio of the polymerizable compound of polymerizable compound, particularly Formulas I or its minor in the most whole mixture It is 0.05～5%, preferably 0.1～the liquid crystal media of 1%.

T) 1～8, preferably 1～5 kind of formula CY1, the liquid crystal media of compound of CY2, PY1 and/or PY2 is comprised.These chemical combination Thing ratio in whole mixture is preferably 5～60%, particularly preferably 10～35%.The content of each compound described is often Plant and under situation, be preferably 2～20%.

U) 1～8, preferably 1～5 kind of formula CY9, the liquid crystal media of compound of CY10, PY9 and/or PY10 is comprised.These are changed Compound ratio in whole mixture is preferably 5～60%, particularly preferably 10～35%.The content of each compound described exists 2～20% it are preferably under every kind of situation.

V) 1～10, preferably 1～the compound of 8 kind of formula ZK, the particularly compound of formula ZK1, ZK2 and/or ZK6 is comprised Liquid crystal media.These compounds ratio in whole mixture is preferably 3～25%, particularly preferably 5～45%.Described each The content of compound is preferably 2～20% in each case a.

W) its Chinese style CY, PY and ZK compound ratio in whole mixture more than 70%, preferably more than 80% Liquid crystal media.

X) PSA-VA display, wherein pre-tilt angle preferably≤85 °, particularly preferably≤80 °.

Second preferred embodiment in, liquid crystal media comprises based on the compound with positive dielectric anisotropy Liquid crystal host mixture.This liquid crystal media be particularly suitable for PSA-OCB, PSA-TN, PSA-positivity-VA, PSA-IPS or Person's PSA-FFS display.

Particularly preferably this second preferred embodiment in liquid crystal media, it comprises one or more selected from formula The compound of AA and BB:

And optionally, in addition to the compound of formula AA and/or BB, the also compound of one or more formulas CC:

Wherein each group has a following meanings:

The most independently of one another, and occur every time Shi Xiangtong or differently represent

Each the most independently of one another, and when occurring every time identical or differently represent

R²¹、R³¹、R⁴¹And R⁴²Represent that there is the alkyl of 1 to 9 carbon atom, alkoxyl, oxa alkyl the most independently of one another Or fluoro-alkyl or there is the thiazolinyl of 2 to 9 carbon atoms,

X⁰Represent F, Cl or there is the alkyl of halogenation or the alkoxyl of 1 to 6 carbon atom, or there are 2 to 6 carbon atoms The thiazolinyl of halogenation or thiazolinyl epoxide,

Z³¹Expression-CH₂CH₂-、-CF₂CF₂-,-COO-, trans-CH=CH-, trans-CF=CF-,-CH₂O-or singly-bound, Preferably-CH₂CH₂-,-COO-, trans-CH=CH-or singly-bound, particularly preferably-COO-, trans-CH=CH-or singly-bound,

Z⁴¹、Z⁴²Expression-CH₂CH₂-,-COO-, trans-CH=CH-, trans-CF=CF-,-CH₂O-、-CF₂O-,-C ≡ C-or Singly-bound, preferably singly-bound,

L²¹、L²²、L³¹And L³²Represent H or F,

G represents 1,2 or 3,

H represents 0,1,2 or 3.

X⁰Preferably F, Cl, CF₃、CHF₂、OCF₃、OCHF₂、OCFHCF₃、OCFHCHF₂、OCFHCHF₂、OCF₂CH₃、 OCF₂CHF₂、OCF₂CHF₂、OCF₂CF₂CHF₂、OCF₂CF₂CHF₂、OCFHCF₂CF₃、OCFHCF₂CHF₂、OCF₂CF₂CF₃、 OCF₂CF₂CClF₂、OCClFCF₂CF₃Or CH=CF₂, particularly preferred F or OCF₃。

The compound of formula AA is preferably selected from following formula:

Wherein A²¹、R²¹、X⁰、L²¹And L²²There is the implication shown in formula AA, L²³And L²⁴Each represent the most independently of one another H or F, and X⁰Preferably represent F.Particularly preferably formula AA1 and the compound of AA2.

The compound of particularly preferred formula AA1 is selected from following minor:

Wherein R⁰Have in formula AA1 for R²¹The implication specified, X⁰、L²¹And L²²There is the implication shown in formula AA1, L²³、 L²⁴、L²⁵And L²⁶Represent H or F, and X the most independently of one another⁰Preferably represent F.

The compound of formula AA1 very particularly preferably is selected from following minor:

Wherein R⁰Have in formula AA1 for R²¹The implication specified.

The compound of particularly preferred formula AA2 is selected from following minor:

Wherein R⁰Have in formula AA1 for R²¹The implication specified, X⁰、L²¹And L²²There is the implication shown in formula AA, L²³、 L²⁴、L²⁵And L²⁶Represent H or F, and X the most independently of one another⁰Preferably represent F.

The compound of formula AA2 very particularly preferably is selected from following minor:

Wherein R⁰Have in formula AA1 for R²¹The implication specified.

The compound of particularly preferred formula AA3 is selected from following minor:

Wherein R⁰Have in formula AA1 for R²¹The implication specified, X⁰、L²¹And L²²There is the implication shown in formula AA3, and X⁰ Preferably represent F.

The compound of particularly preferred formula AA4 is selected from those of following minor:

Wherein R⁰Have in formula AA1 for R²¹The implication specified.

The compound of formula BB is preferably selected from following minor:

Wherein A³¹、A³²、R³¹、X⁰、L³¹、L³²With g, there is the implication shown in formula BB, and X⁰Preferably represent F.Particularly preferably Be the compound of formula BB1 and BB2.

The compound of particularly preferred formula BB1 is selected from following minor:

Wherein R³Have in formula BB1 for R³¹The implication specified, X⁰、L³¹And L³²There is the implication shown in formula BB1, and X⁰ Preferably represent F.

The compound of formula BB1a very particularly preferably is selected from following minor:

Wherein R³Have in formula BB1 for R³¹The implication specified.

The compound of formula BB1b very particularly preferably is selected from following minor:

Wherein R³Have in formula BB1 for R³¹The implication specified.

The compound of particularly preferred formula BB2 is selected from following minor:

Wherein R⁰Have in formula BB2 for R³¹The implication specified, X⁰、L³¹And L³²There is the implication shown in formula BB2, L³³、 L³⁴、L³⁵And L³⁶Represent H or F, and X the most independently of one another⁰Preferably represent F.Particularly preferably formula BB1 and the chemical combination of BB2 Thing.

The compound of formula BB2a very particularly preferably is selected from following minor:

Wherein R³Have in formula BB2 for R³¹The implication specified.

The compound of formula BB2b very particularly preferably is selected from following minor:

Wherein R³Have in formula BB2 for R³¹The implication specified.

The compound of formula BB2c very particularly preferably is selected from following minor:

Wherein R³Have in formula BB2 for R³¹The implication specified.

Formula BB2d very particularly preferably and the compound of BB2e are selected from following minor:

Wherein R³Have in formula BB2 for R³¹The implication specified.

The compound of formula BB2f very particularly preferably is selected from following minor:

Wherein R³Have in formula BB2 for R³¹The implication specified.

The compound of formula BB2g very particularly preferably is selected from following minor:

Wherein R³Have in formula BB2 for R³¹The implication specified.

The compound of formula BB2h very particularly preferably is selected from following minor:

Wherein R³Have in formula BB2 for R³¹The implication specified.

The compound of formula BB2i very particularly preferably is selected from following minor:

Wherein R³Have in formula BB2 for R³¹The implication specified.

The compound of formula BB2k very particularly preferably is selected from following minor:

Wherein R³Have in formula BB2 for R³¹The implication specified.

Alternatively or in addition to the compound of formula BB1 and/or BB2, liquid crystal media can comprise one or more such as The compound of formula BB3 of upper definition.

The compound of particularly preferred formula BB3 is selected from following minor:

Wherein R³Have in formula BB3 for R³¹The implication specified.

In addition to the compound of formula AA and/or BB, the liquid crystal media of this second preferred implementation preferably comprise one or Multiple have dielectric anisotropy dielectric neutral compound in the range of-1.5 to+3, is preferably selected from formula CC as defined above Compound.

The compound of particularly preferred formula CC is selected from following minor:

Wherein R⁴¹And R⁴²There is the implication shown in formula CC, and represent that there is 1 to 7 the most independently of one another The alkyl of carbon atom, alkoxyl, fluoro-alkyl or fluoroalkyl, have the thiazolinyl of 2 to 7 carbon atoms, alkenyloxy group, alkoxyl Alkyl or fluoro thiazolinyl, and L⁴Represent H or F.

In addition to the dielectric neutral compound of formula CC or replace the dielectric neutral compound of formula CC, this second is preferable to carry out The liquid crystal media of mode preferably comprises one or more dielectric anisotropies dielectric neutral compound in the range of-1.5 to+3, Compound selected from formula DD

Wherein A⁴¹、A⁴²、Z⁴¹、Z⁴²、R⁴¹、R⁴²With h, there is the implication shown in formula CC.

The compound of particularly preferred formula DD is selected from following minor:

Wherein R⁴¹And R⁴²There is the implication shown in formula DD, and R⁴¹Preferably represent alkyl, and R in formula DD1⁴²Preferably table Show thiazolinyl, preferably-(CH₂)₂-CH=CH-CH₃, and R in formula DD2⁴²Preferably represent alkyl ,-(CH₂)₂-CH=CH₂Or- (CH₂)₂-CH=CH-CH₃。

Preferably make with the concentration of 2% to 60%, more preferably 3% to 35% and very particularly preferably the 4% to 30% of whole mixture With formula AA and the compound of BB.

Preferably with 2% to 70%, more preferably 5% to 65%, even more preferably the 10% to 60% of whole mixture and the most special Preferably from 10%, preferably concentration from 15% to 50% use formula CC and the compound of DD.

The combination of the liquid crystal host mixture of above-mentioned preferred implementation and liquid-crystal compounds and the above-mentioned compound being polymerized, According to the liquid crystal media of the present invention achieves low threshold voltage, low rotary viscosity and extraordinary low-temperature stability, Keep high clearing point and high HR value simultaneously, and be allowed in PSA display rapidly adjusting the lowest pre-tilt angle. Especially, relative to the medium of prior art, this liquid crystal media demonstrates the response time of notable shortening in PSA display, Particularly also has the gray-tone response time.

This liquid crystal compound preferably has the nematic phase range of at least 80K, the most at least 100K, and at 20 DEG C It is not higher than down the rotary viscosity of 250mPa s, preferably no higher than 200mPa s.

In the VA-type liquid crystal display according to the present invention, the molecule in liquid crystal media layer is perpendicular in the power-off state Electrode surface (vertical plane ground) or with tilting vertical plane (English " tilted ") orientation.When applying voltage to electrode, there is liquid crystal The reorientation of molecule, its molecule longitudinal axis is parallel to electrode surface.

According to the present invention first preferred embodiment, according to the present invention based on having negative dielectric anisotropy Liquid crystal media (especially in PSA-VA escope), has under 20 DEG C and 1kHz preferably about-0.5 to-10, especially The negative dielectric anisotropy on ground about-2.5 to-7.5.

Birefringence n in the liquid crystal media of VA escope according to the present invention is preferably less than 0.16, the most excellent Selection of land is between 0.06 and 0.14, especially between 0.07 and 0.12.

In the OCB-escope according to the present invention, the molecule in liquid crystal media layer has " bending " orientation.Execute During making alive, the reorientation of liquid crystal molecule occurring, its molecule axis oriented normal is in electrode surface.

According to second preferred embodiment, according to the liquid crystal media in PSA-OCB escope of the present invention It is preferably based on those of compound with positive dielectric anisotropy, and preferably has under 20 DEG C and 1kHz preferably about The positive dielectric anisotropy Δ ε of+4～+17.

According to birefringence n in the liquid crystal media of OCB escope of the present invention preferably 0.14 and 0.22 Between, especially between 0.16 and 0.22.

According to second preferred embodiment, according to the present invention based on the compound with positive dielectric anisotropy Liquid crystal media (in PSA-TN, PSA-positivity-VA, PSA-IPS or PSA-FFS escope), preferably have+2～+ 30, the positive dielectric anisotropy of especially+3～+20.

At the liquid crystal in PSA-TN, PSA-positivity-VA, PSA-IPS or PSA-FFS escope according to the present invention In medium, birefringence n is preferably between 0.07 and 0.15, especially between 0.08 and 0.13.

Liquid crystal media according to the present invention can also comprise further to known to those skilled in the art and be described in Additive in document or auxiliary agent, such as polymerization initiator, inhibitor, stabilizer, surfactant, nano-particle or hands Property adulterant.These can be polymerisable or the most polymerisable.Corresponding with this, polymerisable additive is sorted out into gathering The component closed or component A).Correspondingly, the most polymerisable additive is sorted out into the most polymerisable component or component B).

Liquid crystal media can comprise such as one or more chiral dopants, is preferably selected from those of compound of following table B.

In addition the pleochroism dyestuff of such as 0 to 15 weight % can be added liquid crystal media, and also nano-particle, lead Electricity salt preferred 4-hexyloxybenzoate ethyl dimethyl dodecyl base ammonium, tetraphenylboronic acid TBuA or the complex salt of crown ether (such as with reference to Haller etc., Mol.Cryst.Liq.Cryst.24, 249-258 (1973)) and improve electric conductivity, or be used for changing Become dielectric anisotropy, viscosity and/or the material of nematic phase orientation.This kind of substance description in such as DE-A-2209127, 2240864, in 2321632,2338281,2450088,2637430 and 2853728.

The preferred implementation a) of the liquid crystal media according to the present invention～each component z) or known, or ability Field technique personnel can derive their preparation method the most from the prior art, because they are based on described in document Standard method.Corresponding formula CY compound is described in such as EP-A-0364538.Corresponding formula ZK compound is described in example In DE-A-2636684 and DE-A-3321373.

Can prepare, such as by by one or many in the way of liquid crystal media used according to the invention is traditional with itself Kind of above-claimed cpd and one or more polymerizable compounds as defined above, and optionally with other liquid-crystal compounds and/ Or additive mixing.Generally, it would be desirable to quantity, the component that uses with lesser amt is dissolved in and constituted the component of main component In, carry out at elevated temperatures in accordance with destination.Also be able to blending ingredients in organic solvent, such as acetone, chloroform or Solution in methanol, and the most such as remove solvent again by distillation.The invention still further relates to preparation according to this The method of the liquid crystal media of invention.

To those skilled in the art without it should be noted that, can also comprise wherein according to the liquid crystal media of the present invention The compound that such as H, N, O, Cl, F have been replaced by corresponding isotope.

The structure of the liquid crystal display according to the present invention corresponding to geometry conventional for PSA display, as Described in prior art cited during beginning like that.Preferably without protruding geometry, the most additionally at color filter Electrode on side electrically unstructured and only the electrode on TFT side there are those of otch.Particularly suitable and preferred PSA- The electrode structure of VA display is described in such as US2006/0066793A1.

Examples below elaborates the present invention, but is not limited.But, they give those skilled in the art Show that there is the compound that is preferably used and the preferred mixture design of its each concentration and its combination with one another.Separately Outward, these embodiments elaborate to obtain which kind of performance and combining properties.

Use and abridge as follows:

(n, m, z: each represent 1,2,3,4,5 or 6 independently of one another)

Table A

The present invention preferred embodiment in, comprise one or more selected from Table A according to the liquid crystal media of the present invention The compound of compound.

Table B

Table B shows the possible chiral dopant that may be added to according in the liquid crystal media of the present invention.

This liquid crystal media preferably comprises 0～10 weight %, especially 0.01～5 weight % and particularly preferred 0.1～3 weights The adulterant of amount %.This liquid crystal media preferably comprises one or more adulterants selected from the compound of table B.

Table C

Table C shows the possible stabilizer that may be added to according in the liquid crystal media of the present invention.

(representing integer 1～12, preferably 1,2,3,4,5,6,7 or 8 at this n, terminal methyl group does not shows).

This liquid crystal media preferably comprises 0～10 weight %, especially 1ppm～5 weight % and particularly preferably 1ppm～1 The stabilizer of weight %.This liquid crystal media preferably comprises one or more stabilizers selected from the compound of table C.

Table D

Table D shows can be used for according in the liquid crystal media of the present invention preferably as the example of reactive mesogen compound Compound.

In one preferred embodiment of the present invention, mesogenic media comprises one or more chemical combination selected from table D Thing.

It addition, have employed following abbreviation and symbol:

V₀Threshold voltage, capacitive character [V], at 20 DEG C,

n_eExtraordinary refractive index under 20 DEG C and 589nm,

n_oThe ordinary index of refraction under 20 DEG C and 589nm,

Δ n optical anisotropy under 20 DEG C and 589nm,

ε_⊥The dielectric susceptibility of director it is perpendicular under 20 DEG C and 1kHz,

ε | | it is parallel to the dielectric susceptibility of director under 20 DEG C and 1kHz,

Dielectric anisotropy under Δ ε 20 DEG C and 1kHz,

Kp., T (N, I) clearing point [DEG C],

Rotary viscosity [mPa.s] at γ 120 DEG C,

K₁Elastic constant, " tiltedly exhibition (the splay) " deformation [pN] at 20 DEG C,

K₂Elastic constant, " distortion " deformation [pN] at 20 DEG C,

K₃Elastic constant, " bending " deformation [pN] at 20 DEG C,

Unless explicitly pointed out on the contrary, all concentration in the application are given with percentage by weight, and with accordingly Comprise all solids or liquid crystal components and there is no the whole mixture meter of solvent.

Unless expressly stated otherwise, the value of all temperature indicated in this application, such as fusing point T (C, N), from smectic (S) Arrive the transformation T (S, N) and clearing point T (N, I) of nematic (N) phase mutually, all represent with Celsius temperature (DEG C).Fp. fusing point is represented, Kp.=clearing point.Additionally, K=crystalline state, N=nematic phase, S=smectic phase and I=isotropic phase.Tables of data between these symbols Show transition temperature.

All physical properties are based on " Merck Liquid Crystals, Physical Properties of Liquid Crystals ", Status1997 November, Merck KGaA(Germany) measure and Applicable temperature 20 DEG C, and Δ N determines, unless explicitly pointed out on the contrary under every kind of situation at 1 khz with Δ ε under 589nm.

For the present invention, term " threshold voltage " refers to capacitive character threshold value (V₀), also referred to as Freedericksz-threshold Value, unless explicitly pointed out on the contrary.In embodiment, as usual, it is also possible to describe the optics threshold for 10% relative contrast Value (V₁₀)。

For measuring the display of capacitive character threshold voltage by the parallel glass support plate of two planes being spaced apart 20 μm Constituting, described support plate is respectively provided with electrode layer and is positioned at thereon, the most rubbed polyimides composition within it Oriented layer, it causes the edge orientation of vertical plane of liquid crystal molecule.

For measuring the display at inclination angle or testing cassete by the parallel glass support plate structure of two planes being spaced apart 4 μm Becoming, described support plate is respectively provided with electrode layer on inner side and is positioned at the oriented layer that polyimides thereon is constituted, Qi Zhongsuo State two polyimide layers anti-parallel from (antiparallel) through rubbing against one another and cause the edge of vertical plane of liquid crystal molecule Orientation.

By making polymerizable compound at display with the UVA light of certain strength (usual 365nm) the irradiation scheduled time or Testing cassete is polymerized, wherein applies voltage (usually 10V～30V alternating current, 1kHz) to display simultaneously.In embodiment, if Without illustrating on the contrary, use 50mW/cm²Mercury vapor lamp, use equipped with the band filter under 365nm (Bandpassfilter) standard UV gauge (Ushio UNI model gauge) measures intensity.

Inclination angle is determined by rotating crystal test (Autronic-Melchers TBA-105).Here, little value is (i.e. Big deviation relative to 90 ° of angles) corresponding to big inclination.

VHR value is measured as follows: the polymerisable monomer compound by 0.3% adds liquid crystal host mixture, and will The mixture being consequently formed is packed in TN-VHR testing cassete (90 ° of frictions, TN polyimide alignment layers, layer thickness d ≈ 6 μm). At 100 DEG C, under 1V, 60Hz, 64 μ s pulses, before and after UV exposes 2h (sun test) to the open air, after 5min, measure HR value (survey Measuring appratus: Autronic-Melchers VHRM-105).

In order to study low-temperature stability, also referred to as " LTS ", the most at low temperatures liquid crystal compound knot spontaneous for single component The stability that partial crystallization goes out, is placed in-10 DEG C of storages by the bottle of the FK/RM-mixture containing 1g, and whether makes regular check on compound Crystallization.

Embodiment 1

Prepare compound 1 as follows:

1.13-(4-bromophenyl) propane-1-alcohol

First 3-(4-bromophenyl) propanoic acid of 30.0g (0.128mol) is introduced in the THF of 300ml, and under ice-cooling The solution of the hydroboron of dropping 257ml (0.257mol) 1M in THF.Batch of material is made to be stirred at room temperature overnight, cooling Under hydrolyze carefully, and with MTB ether extract three times.The organic facies merged with saturated nacl aqueous solution washing, and via sodium sulfate It is dried.Solvent removed in vacuo, and with MTB ether via silica gel filtered residue.Obtain 3-(4-bromophenyl) propane-1-alcohol, by it Purify the most further and use in next step.

1.23-[4-(4,4,5,5-tetramethyl-[1,3,2]-dioxaborolanes-2-base) phenyl] propane-1-alcohol

By 3-(4-bromophenyl) propane-1-alcohol and double (pinacols of 36.0g (0.139mol) of 26.5g (0.123mol) Closing) two boron are dissolved in the dioxane of 400ml, are adding the potassium acetate of 36.5g (0.372mol) and 2.80 (3.82mmol) After [1,1'-double (diphenyl phosphinidene) ferrocene] palladium chloride (II), heated overnight at reflux.The salt subsequently batch of material diluted Acid acidifying also extracts three times with MTB ether.Wash the organic facies of merging with water, be dried via sodium sulfate and be concentrated in vacuo.With heptane/ MTB ether (4:1) is via silica gel filtered residue, and removes double (pinacol conjunction) two boron at 160 DEG C in fine vacuum.Obtain Huang 3-[4-(4,4,5,5-tetramethyls-[1,3, the 2]-dioxaborolanes-2-base) phenyl] propane-1-alcohol of color oily, it is right It is sufficiently pure for reaction further.

1.33-(4'-bromo-3'-fluorodiphenyl-4-base) propane-1-alcohol

First by 18g (65mmol) sodium metaborate eight hydrate and double (triphenylphosphine) palladiums (II) of 2.8g (3.9mmol) Chloride is incorporated in 200ml water and 100ml THF, adds the bromo-2-of 1-fluoro-4-iodobenzene, drips 21.5g subsequently (0.082mol) 3-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolanes-2-base) phenyl] propane-1-alcohol exists Solution in 100ml THF.By this batch of material heated overnight at reflux, pour in MTB ether and wash three times with water.It is dried via sodium sulfate Organic facies, solvent removed in vacuo.The chromatography carrying out thick product by toluene/ethyl acetate (7:1) on silica gel obtains water white oil 3-(the 4'-bromo-3'-fluorodiphenyl-4-base) propane-1-alcohol of shape.

¹H-NMR(300MHz,CDCl₃):

δ=1.93ppm(m_c,2H,CH₂),2.76(dd,J=7.4Hz,J=8.7Hz,2H,Ar-CH2-),3.71(dd,J= 6.1Hz,J=11.2Hz,2H,-CH₂OH),7.2-7.4(m,4H,Ar-H),7.47(AB-m_c,2H,Ar-H),7.57(dd,J= 7.3Hz,J=8.3Hz,1H,Ar-H)。

The fluoro-4''-of 1.42,2'-bis-(3-hydroxypropyl)-[1,1', 4', 1''] terphenyl-4-alcohol

First by sodium metaborate eight hydrate and double (triphenylphosphine) palladiums of 1.3g (1.8mmol) of 16.5g (59mmol) (II), during chloride is incorporated into 150ml water and 50ml THF, 3-(the 4'-bromo-3'-fluoro connection of 12.5g (38.5mmol) is added Benzene-4-base) propane-1-alcohol, drip the fluoro-4-of 3-(4,4,5,5-tetramethyls-[1,3,2]-two of 12.5g (0.053mol) subsequently Oxa-ring pentaborane-2-base) phenol solution in 50ml THF.By this batch of material heated overnight at reflux, pour in MTB ether and use Wash three times.It is dried organic facies, solvent removed in vacuo via sodium sulfate, thick product is heavily tied from toluene/ethyl acetate (9:1) Brilliant.Obtain the fluoro-4''-of 2,2'-bis-(3-hydroxypropyl)-[1,1', 4', the 1''] terphenyl-4-alcohol of clear crystal form.

The fluoro-4''-of 1.52-methacrylic acid-2,2'-two [3-(2-methacryloxy) propyl group]-[1,1';4', 1''] terphenyl-4-base ester (1)

First by the fluoro-4''-of 2,2'-bis-(3-hydroxypropyl)-[1,1', 4', the 1''] terphenyl-4-of 3.0g (8.81mmol) Alcohol is incorporated in the dichloromethane of 60ml, adds the triethylamine of 4ml, and drips 2.2ml under ice cooling, 4 (22.5mmol) acryloyl chloride solution in 5ml dichloromethane.Remove cooling, batch of material is stirred at room temperature 3 hours.With Filter this solution by by silica gel, concentrate and by residue from ethyl alcohol recrystallization.Obtain the clear crystal form that fusing point is 67 DEG C The fluoro-4''-of 2-methacrylic acid-2,2'-two [3-(2-methacryloxy) propyl group]-[1,1';4', 1''] terphenyl- 4-base ester (1).

Embodiment 2

Prepare compound 2 as follows:

The fluoro-4''-of 2.12'-(3-hydroxypropyl)-[1,1';4', 1''] terphenyl-4-alcohol

Be similar to the synthesis described in 1.4, by 3-(4'-bromo-3'-fluorodiphenyl-4-base) propane-1-alcohol and 4-(4,4, 5,5-tetramethyl-[1,3,2] dioxaborolanes-2-base) phenol obtains 2'-fluoro-4''-(the 3-hydroxypropyl of colorless solid form Base)-[1,1';4', 1''] terphenyl-4-alcohol.

¹H-NMR(400MHz,DMSO-d₆)

δ=1.80ppm(m_c,2H,CH₂),2.71(7,J=7.8Hz,2H,Ar-CH₂-),3.71(7,J=6.5Hz,2H,- CH₂OH),4.53(s,br.1H,OH),6.93(AB-m_C, 2H, Ar-H), 7.35 (d, J=8.25,2H, Ar-H), 7.47 (AB-dd, J=1.5Hz,J=8.6Hz,2H,Ar-H),7.54-7.64(m,3H,Ar-H),7.70(d,J=8.3Hz,2H,Ar-H),9.70(s, 1H,Ar-OH)。

The fluoro-4''-of 2.22-methacrylic acid-2'-[3-(2-methacryloxy) propyl group]-[1,1';4', 1''] three Biphenyl-4-base ester (2)

It is similar to embodiment 1, by the fluoro-4''-of 2'-(3-hydroxypropyl)-[1,1';4', 1''] terphenyl-4-alcohol obtains fusing point Be the clear crystal form of 76 DEG C the 2-fluoro-4''-of methacrylic acid-2'-[3-(2-methacryloxy) propyl group]-[1, 1';4', 1''] terphenyl-4-base ester (2).

Embodiment 3-7

The method described in embodiment 1 and 2 that is similar to prepares following compound:

(wherein D represents deuterium)

Mixture embodiment A

Nematic liquid crystal mixture N1 prepares as follows:

In each case, the polymerisable monomer of the formula 1,2,3,4,5 or 6 from embodiment 1-6 of 0.3% is added liquid In brilliant mixture N1.Thus obtained mixture is introduced VAe/o testing cassete, and (through antiparallel friction, VA-polyimides takes To layer, layer thickness d ≈ 4 μm).By this box 50mW/cm under the voltage condition applying 24V (alternating current)²The UV illumination of intensity Penetrate the shown time, so that monomeric compound is polymerized.Before and after UV irradiates, tested by rotating crystal (Autronic-Melchers TBA-105) measures inclination angle.

In order to measure rate of polymerization, after different time of exposure in testing cassete the surplus of unconverted monomer (in terms of weight %) uses HPLC method to measure.To this end, every kind of mixture is polymerized respectively under the conditions of shown in testing cassete. Then mixture use MEK (butanone) wash out from testing cassete and measure.

Additionally, the liquid crystal media for comprising liquid crystal compound N1 and monomer 1 or 2 determines liquid crystalline phase by dsc measurement Character, and the LTS at-10 DEG C determined as described above and the VHR value before and after sunlight test exposure 2h.

For comparison purposes, known polymerizable chemical combination from prior art (such as WO2009/030329A1) is used Thing V1 and V2 tests as above.

Inclination angle comparative result for monomer 1-6 and V1 and V2 shows in Table 1.

Table 1 (t=time of exposure)

As it can be seen from table 1 at the same terms (50mW/cm²,UVA;Under 24V), it is situated between with the liquid crystal with N1 and monomer V1 Matter is compared, at the PSA display of the liquid crystal media comprising one of liquid crystal compound N1 and monomer 1-6 containing the with good grounds present invention In, significantly faster obtain the generation at inclination angle.

With 50mW/cm²After exposure, 2min and 24V voltage, the PSA in liquid crystal compound N1 with monomer V1 shows That shows inclination angle in device is changed to such as 1.1 °.Under similarity condition, the PSA of the monomer 1 containing the with good grounds present invention in N1 shows In the case of showing device, tilt angle varied is 4.8 °, is 4 times；There is in N1 the situation inclination angle of monomer 2 according to the present invention It is changed to 8.1 °, is 7 times.In both embodiments, even if it is observed that inclination angle saturated after 240s (4 minutes). For monomer V1 really not so.

After various time of exposure, the monomer concentration in display is as shown in table 2.

Table 2 (t=time of exposure)

Difference on residual monomer content is the most noticeable.As it can be observed from fig. 2 that have monomer in N1 In the PSA display of V1, after exposure 360s (6 minutes), the monomer of initial 0.3% still has 0.241%.On the contrary, in identical exposure After the light time, such as, have in N1 in the PSA display of the monomer 1 according to the present invention and only contain only initial 0.3% 0.082%, and such as have in N1 those of the monomer 2 according to the present invention only contain only initial 0.3% 0.037% residue single Body.

E function goes for the measurement data curve to time of exposure of content of monomer.By its available exponential factor C, it is the tolerance (seeing table 2) of rate of polymerization.Therefore, fast 7 times of the polymerization than the monomer V1 in N1 of the monomer 1 in N1, and Fast 12 times of the polymerization than the monomer V1 in N1 of the monomer 2 in N1.

LTS and the VHR value of Mesomorphic behavior and liquid crystal base is shown in table 3.

Table 3

As can be seen from Table 3, LTS and the VHR value of the monomer 1-6 according to the present invention in liquid-crystal compounds N1 is also The most excellent, and can match in excellence or beauty or even LTS and VHR value than the monomer V1 in N1 is more preferable.

Although monomer V2 demonstrates than the pre-tilt even faster of the monomer 1-6 according to the present invention in liquid crystal compound N1 Produce (seeing table 1) and rate of polymerization (seeing table 2) even faster, but its unusual indissoluble cause liquid crystal/monomer to mix Thing before exposure and the most poor LTS and VHR value, can be seen that in table 3.

Claims (5)

1. the compound of Formulas I

Wherein

P^a,P^bEach represent acrylate-based or methacrylic acid ester group independently of one another,

When Sp occurs every time identical or differently selected from formula Sp "-X " so that group " P^a/b-Sp-" corresponding to formula " P^a/b-Sp”- X "-", wherein-Sp "-X "-it is-(CH₂)_p1-、-(CH₂)_p1-O-、-(CH₂)_p1-O-CO-、-(CH₂)_p1-O-CO-O-, wherein p1 is The integer of 1-12,

L¹,L²,L³Represent F or Cl, group L the most independently of one another¹、L²And L³In one or more also illustrating that have 1,2 or 3 The alkyl being completely or partially fluorinated of individual carbon atom or alkoxyl, P^aOr P^a-Sp-, wherein group L¹、L²And L³In extremely Few one represents F or Cl,

R1, r2, r3 represent 0,1,2,3 or 4 the most independently of one another, wherein

R1+r2+r3 >=1,

And one of s1 and s2 represents another expression 1 of 0 and s1 and s2.

Compound the most according to claim 1, wherein group L¹、L²And L³In at least one represent F.

Compound the most according to claim 1, it is selected from following minor:

Wherein P^a、P^bWith Sp, there is the implication shown in claim 1 and s1 represents 1.

4. the compound of formula II

Wherein Sp, L¹、L²、L³, r1, r2 and r3 there is the implication shown in claim 1 or 2, and G and G' is the most independent of one another Ground represents H atom.

5. for the method preparing the compound according to any one of claims 1 to 3, wherein by chemical combination according to claim 4 Thing in the presence of a dehydrating agent, with containing group P^aOr P^bCorresponding acid, acid derivative or halogenated compound esterification or etherificate.